TWI737911B - Device of generating hydrogen through hydrolysis along with reduction of carbon dioxide - Google Patents

Abstract

A device is provided to generate hydrogen through hydrolysis while carbon dioxide is reduced. The device comprises a first panel of a translucent material; a first electrode deposed at an end under the first panel; a separator membrane deposed under the first panel; a second electrode deposed under the separating membrane; and a third electrode deposed at another end under the first panel. The present invention provides an efficient device to generate hydrogen with methanation. A photocatalytic composite of reforming catalysts is developed. Therein, the composite comprises a titanium-based catalytic material and a metal-, oxide- or metal-oxide-based catalytic material. Its composition include 1~90 weight percent (wt%) of the titanium-based catalytic material and 0~10wt% pf the metal-, oxide- or metal-oxide-based catalytic material. Thus, the composite obtains very high activity and selectivity to be directly applied in both the anode and the cathode. After the catalyst electrodes are deposed under light or applied with heat or bios voltage to hydrolyze water into electrons and holes for generating hydrogen, protons (H+) are directly supplied to the cathode catalyst electrode containing carbon dioxide by passing through the separator membrane; and chemical fuels of hydrocarbons or alcohols, such as methane, methanol or the like, are obtained through reforming reduction of carbon dioxide.

Description

Device with water decomposition to produce hydrogen and carbon dioxide reduction and conversion

The present invention relates to a device that can simultaneously produce hydrogen and convert carbon dioxide (to fuel), in particular to a device that can use light or an external bias to directly split water to produce hydrogen and the hydrogen produced can be directly applied to react with carbon dioxide to produce fuel , In particular, it refers to a water decomposition hydrogen production and carbon dioxide reduction conversion device that provides an application method for the reduction of carbon dioxide and does not require high temperature energy consumption for reaction.

Over 98% of Taiwan’s energy comes from imports, and energy autonomy is low. It is currently facing a mid- to long-term energy transition plan. The government’s new energy policy proposes to achieve 20% renewable energy, 50% natural gas, and 30% coal burning by 2025. The power generation structure must be able to provide stable power supply. Natural gas is one of the three pillars of the world's energy structure. It is also a relatively clean, high-efficiency, low-carbon energy resource. The pollution to the air is much lower than that of coal and oil. Therefore, the use of natural gas to replace coal and oil has become an advanced One of the feasible solutions for the country to reduce carbon dioxide (CO _{2 ).} Natural gas has a wide range of uses, such as power generation, chemical industry, household heating, industrial boilers, and automobile fuels. One of the biggest advances is power generation. The new technology not only reduces the cost of natural gas power generation, but also carbon dioxide emissions can be as much as 50% less than that of coal. In the current world energy consumption structure, natural gas accounts for 24%, while my country's natural gas accounts for less than 5%, which is far below the world average. There is an urgent need to increase natural gas consumption.

Carbon dioxide has a carbon-carbon double bond (C=C), which is very strong. Coupled with oxygen, it has very high stability. Generally, very high external energy is required to break the strong bond of the bond, so additional energy is needed to break it. Its bond. Generally, the external energy required for the reaction can be provided by heating, electrons, and irradiation/photons; then, these processes are called thermochemistry, electrochemistry, and photochemistry, respectively. Therefore, some form of catalysis is necessary. Generally speaking, high pressure and high temperature must be used to reduce the energy barrier.

Taking methanation as an example is the hydrogenation of carbon monoxide and carbon dioxide to produce methane. It is a highly exothermic and reversible reaction. Once the reaction starts, it quickly reaches equilibrium. It means that the carbon monoxide, carbon dioxide and hydrogen in the synthesis gas must undergo a chemical reaction to generate methane under a certain high temperature, high pressure and the action of a catalyst. However, high temperature (generally, the Fischer-Tropsch process in commercial processes usually reacts at 800°C) is usually too energy-consuming and increases the cost; and the design of the reactor under high pressure is a consideration.

CO ₂ (g)+4H ₂ (g)→CH ₄ (g)+2H ₂ O(g)

△H298K=-165kJ/mol

The above reaction is usually carried out between 250°C and 500°C. It is mainly produced by the recombination of carbon dioxide, hydrogenation of carbon dioxide and the reaction of catalysts. Since carbon dioxide is a product of complete combustion and its thermodynamic properties are very stable, the use of carbon dioxide as a reaction material will face the problem of thermodynamic limitations, but if it can react with other substances with higher Gibbs Free Energy (Gibbs Free Energy) The raw materials are thermodynamically more favorable, such as methane recombination reaction and hydrogenation reaction. In addition, because carbon dioxide is quite stable, catalysts are often needed to carry out chemical reactions in a relatively mild state, so catalysts also play a very important role.

Related patents include US8815074, US8845878, CN103974897, EP2940102, and CN105038880. Among them, the U.S. US8815074 patent discloses a device for preparing carbon dioxide with its metal organic framework (MOF). Set, and apply voltage between different cathodes and anodes to reduce carbon dioxide. The applied voltage is from -1.4V to 1.2V, and the reaction is carried out in 0.5M potassium bicarbonate solution. The main product of choice is formic acid. The US8845878 patent discloses that in potassium chloride (KCl) and other solutions, various special catalysts are used to apply different voltages from -0.5V to 2V, and produce different compounds and chemicals between pH 4-8. Therefore, carbon dioxide reduction conversion technology is currently mostly a conversion process that requires additional energy to be carried out in a liquid solution, which faces the problem of energy consumption, and the complexity and stability of the device must be broken.

Carbon dioxide conversion is a forward-looking science and technology that is actively developed by countries all over the world. However, advanced countries are still at the stage of technological development, testing and verification, and no commercial operation system has come out, and my country has not yet developed a simultaneous decomposition system. Reduction and conversion into fuel device. Therefore, general users cannot meet the needs of users in actual use.

The main purpose of the present invention is to overcome the above-mentioned problems encountered by the prior art and provide an efficient hydrogen production and methanation system, mainly using a self-developed photocatalytic composite conversion catalyst, which is characterized by being made of titanium Catalytic material is compounded with metal, oxide, or metal oxide-based catalytic material. The composition is titanium-based catalytic material 1~90wt%, and metal, oxide or metal oxide-based catalytic material is up to 10wt%, which has quite high activity And selectivity, it can be directly placed in the positive and negative electrodes of the device. After the catalyst electrode is illuminated, heated or biased, the aqueous solution is decomposed to produce electron holes and hydrogen gas (H ₂ ) is generated. After the protons (H ⁺ ) pass An isolation membrane is directly supplied to the cathode catalyst electrode containing carbon dioxide for reduction and conversion into hydrocarbon or alcohol chemical fuels, such as methane or methanol.

The secondary objective of the present invention is to provide a device that uses direct illumination, heating or bias voltage reduction device to decompose and reduce water into hydrogen and methane fuel, which can effectively treat carbon dioxide and reduce the amount; wherein, the fuel produced can be different Catalytic electrode to make a choice, generate methane Or methanol, etc. for use. The hydrogen produced by this device can also be connected to a fuel cell for power generation. Generally, fuel cells have the advantages of high energy conversion efficiency, low noise during reaction, and low environmental pollution; fuel cells are not a single rechargeable battery that is lost when it is used up, and does not need to be recharged As long as the hydrogen fuel is continuously added, the power generation output can be maintained. The higher the concentration of hydrogen fuel, the longer the operating life of the fuel cell. The carbon dioxide produced after the reaction can also be introduced into the device of the present invention for recycling and conversion. In order to reduce carbon dioxide emissions, it can increase the production of green energy.

Use photocatalyst to reduce carbon dioxide to hydrocarbon or alcohol chemical fuel, that is, use solar energy to split water (H ₂ O) to produce hydrogen or convert carbon dioxide into fuel (hydrogen, carbon monoxide, methanol, methane, etc.). It can be stored and used in the form of energy. The metal catalyst can reduce carbon dioxide-containing water or non-aqueous solution to generate hydrocarbon or alcohol chemical fuel, or carbon dioxide can be converted into organic matter by thermochemical conversion method. Although it is currently a forward-looking science and technology, it is considered to be one of the best ways to convert and utilize solar energy in the future because the converted solar fuel can match the existing energy requirements and structural applications well. Carbon dioxide is a thermodynamically stable compound. The production of carbon dioxide as a raw material is its reduction product. To complete this reaction, the carbon dioxide needs to be activated, that is, the carbon dioxide needs to be imported into the carbon dioxide in the form of high energy. Therefore, the development of low energy consumption of carbon dioxide conversion And utilization technology is of great significance to the establishment of a decarbonized energy system. Artificial photosynthesis is an innovative technology for the conversion and utilization of carbon dioxide. It uses solar energy to excite semiconductor photocatalytic materials to generate electron-hole pairs, and undergo oxidation-reduction reactions to synthesize carbon dioxide with hydrogen or water into hydrocarbon fuels. Compared with other methods, this reaction is carried out under normal temperature and pressure. The raw materials are simple and easy to obtain. The direct use of solar energy does not need to consume additional energy. It can realize the recycling of carbon materials and is considered to be the most promising carbon dioxide conversion method.

To achieve the above objectives, the present invention is a device with water splitting to produce hydrogen and carbon dioxide reduction and conversion, which includes: a first panel, which is a light-permeable material; A photocatalytic composite conversion catalyst film is composed of 1~90wt% of titanium-based catalytic material and up to 10wt% of metal, oxide, or metal oxide-based catalytic material. The distance between the first electrode and the first panel is There is a space to form a space, and the space is provided with an electrolyte layer; an isolation membrane is arranged under the first electrode and is made of a material that allows protons to pass through; a second electrode is arranged under the isolation membrane and is made of 1 ~90wt% of titanium-based catalytic material and up to 10wt% of metal, oxide, or metal oxide-based catalytic material are combined to form a photocatalytic composite conversion catalyst film; and a third electrode disposed under the first panel. One end is composed of 1~90wt% of titanium-based catalytic material and up to 10wt% of metal, oxide, or metal oxide-based catalytic material to form a photocatalytic composite conversion catalyst film, and the first electrode and the third The side surfaces between the electrodes are sealed and fixed by a first separator, and an incompletely sealed second separator is added between the second electrode and the third electrode.

In the above embodiment of the present invention, the first panel is made of quartz, pyrex glass, or transparent acrylic.

In the foregoing embodiment of the present invention, the first, second and third electrode systems are platinum, palladium gold, titanium, zinc oxide, or titanium dioxide.

In the above embodiments of the present invention, the electrolyte layer is an aqueous solution or an electrolyte containing a sacrificial reagent.

In the above embodiments of the present invention, the isolation film is nafion.

In the above embodiment of the present invention, at least one bias wire is arranged between the first electrode and the second electrode.

In the above-mentioned embodiment of the present invention, the first electrode is provided with a sampling port and a sampling port.

In the foregoing embodiment of the present invention, a carbon dioxide injection port and a fuel sampling port are provided at the second electrode.

1: the first electrode

2: second electrode

3: third electrode

4: The first panel

5: Isolation film

6: Carbon dioxide injection port and fuel sampling port

7: Inlet and sampling port

8, 9: Bias wire

10: The first partition

Figure 1 is a schematic top view of an apparatus for hydrogen production by water splitting and reduction and conversion of carbon dioxide according to an embodiment of the present invention.

Figure 2 is a schematic side view of an embodiment of the invention with a water splitting hydrogen production and carbon dioxide reduction conversion device.

The technical means and effects used by the present invention to achieve the purpose will be described below with reference to the accompanying drawings, and the embodiments listed in the following drawings are only an auxiliary explanation for your reviewers’ understanding, but the technical means in this case are not Limited to the schemes listed. Those with ordinary knowledge in the technical field should be able to easily understand the spirit and principle of the present invention by referring to the description and the accompanying drawings. Therefore, for those with ordinary knowledge in the technical field, various changes and modifications to the present invention should be obvious and easily reachable without departing from the spirit and principle of the present invention.

Please refer to "Figure 1 and Figure 2", which are the top view schematic diagrams of a water splitting hydrogen production and carbon dioxide reduction conversion device according to an embodiment of the present invention, and a water splitting hydrogen production according to an embodiment of the present invention. And the schematic side view of the carbon dioxide reduction conversion device. As shown in the figure: the present invention is a device with water decomposition to produce hydrogen and carbon dioxide reduction and conversion, which includes a first panel 4, a first electrode 1, an isolation membrane 5, a second electrode 2, and a third electrode 3 constituted.

The material of the first panel 4 mentioned above is a light-permeable material, such as quartz, Pyrex (pyrex) glass, or transparent acrylic.

The first electrode 1 is arranged at the lower end of the first panel 4, and is composed of 1~90wt% of titanium-based catalytic material and up to 10wt% of metal, oxide, or metal oxide-based catalytic material to form a photocatalytic composite conversion The catalyst film is made of platinum, palladium, gold, titanium, zinc oxide, or titanium dioxide. In this embodiment, it is platinum/titanium dioxide; there is a gap between the transparent first panel 4 and the first electrode 1 to form A space (not shown in the figure), the space is provided with an electrolyte layer (not shown in the figure), and the material can be an aqueous solution or an electrolyte containing a sacrificial reagent. In this embodiment, an aqueous sulfuric acid solution is used. Wherein, the first electrode 1 is further provided with a sampling port and a sampling port 7.

The isolation membrane 5 is disposed between the first electrode 1 and the second electrode 2, and its material is a material that allows protons (H ⁺ ) to pass through. In this embodiment, it is a nafion film.

The second electrode 2 is disposed under the isolation film 5, and is composed of 1~90wt% of titanium-based catalytic material and up to 10wt% of metal, oxide, or metal oxide-based catalytic material to form a photocatalytic composite conversion catalyst The material of the thin film is platinum, palladium gold, titanium, zinc oxide, or titanium dioxide. In this embodiment, it is platinum/titanium dioxide. Wherein, the second electrode 2 is provided with a carbon dioxide injection port and a fuel sampling port 6.

The third electrode 3 is arranged at the other end under the first panel 4, and its material is the same as that of the second electrode 2. It is made of 1~90wt% of titanium-based catalytic material and up to 10wt% of metal, oxide, or metal oxidation The material system catalytic material is compounded into a photocatalytic composite conversion catalyst film, which can increase the reaction conversion rate. In this embodiment, platinum/titanium dioxide is used. Wherein, the side surface between the first electrode 1 and the third electrode 3 is sealed and fixed by a first separator 10, and an incompletely sealed second separator is added between the second electrode 2 and the third electrode 3. (Not shown in the figure) to make unreacted hydrogen react with the third electrode 3. If so, a brand-new hydrogen production and carbon dioxide reduction conversion device with water splitting is constructed by the above-disclosed process.

When used, when light is irradiated on the device with water splitting hydrogen production and carbon dioxide reduction and conversion of the present invention, the first electrode 1 will begin to absorb light energy to decompose the aqueous solution of sulfuric acid into electrons, holes, and protons ( H ⁺ _{) undergoes a reduction conversion reaction with carbon dioxide (CO 2} ) adsorbed on the second electrode 2 through the isolation membrane 5 to form a hydrocarbon or alcohol chemical fuel, such as methane or methanol. When the light intensity is not enough to drive the device of the present invention, a bias wire 8, 9 can be arranged between the first electrode 1 and the second electrode 2; or the temperature during the reaction can be increased to drive the device to transform into The effect of fuel yield.

Direct lighting, heating or bias voltage reduction device water decomposition and reduction into hydrogen (H ₂ ) and methane fuel, effectively processing carbon dioxide and reducing the amount; among them, the fuel produced can be selected according to different catalyst electrodes, Generate methane or methanol for use. The hydrogen produced by this device can also be connected to a fuel cell for power generation. Generally, fuel cells have the advantages of high energy conversion efficiency, low noise during reaction, and low environmental pollution; fuel cells are not a single rechargeable battery that is lost when it is used up, and does not need to be recharged As long as the hydrogen fuel is continuously added, the power generation output can be maintained. The higher the concentration of hydrogen fuel, the longer the operating life of the fuel cell. The carbon dioxide produced after the reaction can also be introduced into the device of the present invention for recycling and conversion. In order to reduce carbon dioxide emissions, it can increase the production of green energy, which can effectively reduce the amount of carbon dioxide and realize the effect of recycling carbon materials.

[Embodiment 1]

Prepare 2.5cm x 2.5cm platinum/titanium dioxide as the first electrode 1, the second electrode 2 and the third electrode 3. Place a nafion isolation film 5 between the first electrode 1 and the second electrode 2 and fix it in the first figure. In the right side of the device shown; fix the third electrode 3 in the left side of the device shown in Figure 1. A sulfuric acid aqueous solution covering the first electrode 1 is injected between the first panel 4 of light-transmitting material and the first electrode 1 as an electrolyte layer. Under the second electrode 2, the purging device is purged with helium (He). After other gases, inject pure carbon dioxide gas (100c.c). The gas temperature setting range is from 30 to 200°C, and the operating time of the entire system is from 1 to 8 hours. Turn on the solar simulator AM1.5, the light-transmitting first panel 4 irradiates the reaction, the operation time is terminated, and samples are taken for gas chromatography (GC) through the sampling ports 6 and 7. After analysis and comparison with the calibration curve, hydrogen can produce 0.2 micromole/hr (μmole/hr) and methane can produce 0.06μmole/hr.

[Embodiment 2]

A III-V cell is connected via external bias wires 8 and 9 as an aid, and the light-transmitting first panel 4 irradiates the reaction, the temperature range is from 25 to 90° C., and the entire reaction time is from 1 to 4 hours.

After the III-V cell is irradiated with AM1.5, the voltage is 2.4 volts (V) and the current is 6.1 milliamps (mA). After the reaction, the gas in the reactor is analyzed and compared with the calibration curve. Hydrogen can produce 1.9μmole/hr, and methane can produce 0.44μmole/hr.

The above results confirm that the device concept of the present invention includes water splitting hydrogen production technology and reductive conversion technology, and this concept can effectively produce hydrogen, methane and other fuels. In the future, green energy such as solar energy will save the original electricity energy consumption and effectively reduce the carbon dioxide content, which will help improve energy independence and reduce the greenhouse effect.

As a result, the water decomposition hydrogen production and carbon dioxide reduction conversion device provided by the present invention can be used mainly with solar energy and other green energy sources to improve its efficiency. The energy of solar energy remaining on the earth every year is about 0.6W/m2, about It is equivalent to 1022 joules per year, which is equivalent to 20 times the global energy consumption for utilization. At the same time, Taiwan’s sunshine hours are long and must be used effectively. If solar energy can be used as energy in the future, low-cost hydrogen can be produced as a source of synthetic methane, which can provide an option for Taiwan’s energy transformation applications. Because it can realize carbon recovery and reduction, so that carbon dioxide can be recycled into resources while effectively controlling the greenhouse effect of carbon dioxide. The object of the present invention is to directly decompose carbon dioxide and then hydrogenate and reduce it, combined with production To methane, other fuels or petrochemical products, this device provides an efficient hydrogen production and methanation system in terms of carbon dioxide reduction, environmental protection and high-value utilization, and chemical manufacturing applications.

In summary, the present invention is a device with water decomposition to produce hydrogen and carbon dioxide reduction and conversion, which can effectively improve the various shortcomings of conventional use. It can use carbon dioxide as a carbon source to convert carbon dioxide into high-value chemicals by chemical or photochemical methods. Or energy products, in addition to greatly reducing the cost of carbon dioxide recovery and subsequent storage problems, can also reduce the dependence on fossil fuels by replacing carbon sources originally required from fossil fuels and more energy-consuming processes, thereby making the present invention Produce that is more advanced, more practical, and more in line with the needs of users, and indeed meets the requirements of an invention patent application, and a patent application is filed in accordance with the law.

However, the above are only the preferred embodiments of the present invention, and should not be used to limit the scope of implementation of the present invention; therefore, all simple equivalent changes and modifications made in accordance with the scope of the patent application of the present invention and the content of the description of the invention , Should still fall within the scope of the invention patent.

1: the first electrode

2: second electrode

3: third electrode

4: The first panel

5: Isolation film

6: Carbon dioxide injection port and fuel sampling port

7: Inlet and sampling port

8, 9: Bias wire

10: The first partition

Claims (7)

A device with water decomposition to produce hydrogen and carbon dioxide reduction and conversion includes: a first panel, which is a light-permeable material; a first electrode, arranged at the lower end of the first panel, and is catalyzed by 1~90wt% titanium The material is combined with up to 10wt% of metal, oxide, or metal oxide-based catalytic material to form a photocatalytic composite conversion catalyst film. There is a distance between the first electrode and the first panel to form a space, the space An electrolyte layer is provided; an isolation membrane is arranged under the first electrode and is ^{made of a material that allows protons (H +} ) to pass through; a second electrode is arranged under the isolation membrane and is made of 1~90wt% titanium The catalytic material is combined with at most 10wt% of metal, oxide, or metal oxide-based catalytic material to form a photocatalytic composite conversion catalyst film, wherein the second electrode is provided with a carbon dioxide injection port and a fuel sampling port; and A third electrode, arranged at the other end under the first panel, is composed of 1~90wt% of titanium-based catalytic material and up to 10wt% of metal, oxide, or metal oxide-based catalytic material to form a photocatalytic composite conversion A catalyst film is used, and the side surface between the first electrode and the third electrode is sealed and fixed with a first separator, and an incompletely sealed second separator is added between the second electrode and the third electrode. According to the first item of the scope of patent application, the device with water splitting for hydrogen production and carbon dioxide reduction and conversion, wherein the first panel is made of quartz, pyrex glass, or transparent acrylic. According to the first item of the scope of patent application, the device for producing hydrogen by water splitting and reducing and converting carbon dioxide, wherein the composition of the first, second and third electrode materials is titanium, platinum, Palladium, zinc oxide, or titanium dioxide. According to the first item of the scope of patent application, the device with water splitting to produce hydrogen and carbon dioxide reduction and conversion, wherein the electrolyte layer is an aqueous solution or an electrolyte containing a sacrificial reagent. According to the first item of the scope of patent application, the device with water splitting for hydrogen production and carbon dioxide reduction and conversion, wherein the isolation membrane is nafion. According to the first item of the scope of patent application, the device with water splitting to produce hydrogen and carbon dioxide reduction and conversion, wherein at least one bias wire is arranged between the first electrode and the second electrode. According to the first item of the scope of patent application, the device with water splitting to produce hydrogen and carbon dioxide reduction and conversion, wherein the first electrode is provided with a sampling port and a sampling port.

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